JP2001064519A - Green resin composition, photosensitive green resin composition, green image forming photosensitive liquid, preparation of colored image and colored filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a light transmittance which is a problem of a photosensitive material dispersing a pigment by using a green pigment with a specific structure and restricting a bromine atom to a certain number. SOLUTION: A green pigment to be used is represented by the formula (wherein X is H, Cl or Br). The number of the bromine atom is from 14 to 16. A resin to be used has no restriction if it has dispersibility of the pigment, and desirably has film-forming properties and developing properties. For example, it is carboxymethylhydroxyethyl cellulose. The resin preferably has an unsaturated equivalent between 200-3,000, and weight-average molecular weight between 1,500-200,000. A preparation of a green resin composition comprised using per 100 pts.wt. of the pigment, 20 pts.wt. of the resin. According to demand, a dispersant (e.g. an anion dispersant) is used. An organic solvent (e.g. diethylene glycol mono or dialky ether) is used and mixed, at dispersion, in 100 pts.wt. thereof per 100 pts.wt. in total of the pigment and the resin to disperse them.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a green resin composition,
The present invention relates to a photosensitive green resin composition, a photosensitive liquid for forming a green image, a method for producing a colored image, and a method for producing a color filter.

[0002]

2. Description of the Related Art In recent years, color filters have been frequently used in liquid crystal display devices, sensors, color separation devices, and the like.

[0003] As a method of manufacturing this color filter,
Conventionally, a method has been adopted in which a dyeable resin, for example, natural gelatin or casein is patterned and dyed therewith mainly using a dye to obtain pixels. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials.

Therefore, recently, a method of using a photosensitive material in which a pigment is dispersed for the purpose of improving heat resistance and light resistance has attracted attention, and much research has been conducted. According to this method, the manufacturing method is simplified, and the obtained color filter is known to be stable and have a long life.

However, when a pigment is used as compared with a dye, there is a problem that the light transmittance is low.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a green resin composition which improves the light transmittance which is a problem of a photosensitive material in which a pigment is dispersed, and which solves the problems of the prior art. It is in.

Another object of the present invention is to provide a photosensitive green resin composition having improved light transmittance.

Another object of the present invention is to provide a green image forming photosensitive liquid having improved transmittance.

Another object of the present invention is to provide a method for producing a colored image with improved light transmittance.

Another object of the present invention is to provide a method for producing a color filter including a green image having excellent light transmittance.

[0011]

According to the present invention, there is provided a green resin composition comprising a green pigment dispersed in a resin, wherein the green pigment has the general formula (I):

[0012]

Embedded image (Wherein, X represents a hydrogen atom, a chlorine atom or a bromine atom), and relates to a green resin composition characterized in that the number of bromine atoms is 14 or more and 16 or less.

According to the present invention, there is also provided a green resin composition comprising a green pigment and a yellow pigment dispersed in a resin, wherein the green pigment is represented by the general formula (I) and the number of bromine atoms is 14 or more.
The present invention relates to a green resin composition having six or less.

The present invention also provides a photosensitive green resin composition comprising a green pigment, a resin, a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator, wherein the green pigment is The present invention relates to a photosensitive green resin composition represented by the general formula (I), wherein the number of bromine atoms is 14 or more and 16 or less.

The present invention also provides a photosensitive green resin composition comprising a green pigment, a yellow pigment, a resin, a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator. The present invention relates to a photosensitive green resin composition, wherein the green pigment is represented by the general formula (I) and the number of bromine atoms is 14 or more and 16 or less.

The present invention also relates to a photosensitive liquid for forming a green image, wherein the photosensitive green resin composition further comprises an organic solvent and components other than the organic solvent are dissolved or dispersed in the organic solvent.

The present invention also relates to a method for producing a colored image, which comprises a colored image forming step of laminating a photosensitive layer comprising the above-described photosensitive green resin composition on a substrate and exposing and developing the photosensitive layer.

The present invention also relates to a method for producing a colored image, in which the photosensitive layer is formed from the above-described photosensitive liquid for forming a green image.

The present invention also relates to a method for producing a color filter, comprising a step of forming a green image by the method for producing a colored image.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, pigments include
General formula (I)

[0021]

Embedded image (Wherein, X represents a hydrogen atom, a chlorine atom or a bromine atom), and a green pigment having 14 to 16 bromine atoms is used as an essential component. When the number of bromine atoms is 13 or less, the transmittance tends to decrease.

As the green pigment in the present invention, other green pigments can be used in addition to the above-mentioned green pigments.
The amount used is from 0 to 90 with respect to the entire green pigment.
% By weight, more preferably 0 to 50% by weight. When the amount of the green pigment other than the green pigment used is too large, the light transmittance tends to decrease.
Examples of other green pigments include green pigments represented by the general formula (I) and having 0 to 13 bromine atoms.

In the present invention, toning may be performed by mixing a yellow pigment with a green pigment. Examples of the yellow pigment used in combination include, for example, Pigment Yellow 17, 20, 24, 83, 93, 109, 110, 1
17, 125, 128, 129, 138, 139, 14
7, 150, 154, 185 and the like. These green pigments and yellow pigments can be used as a mixture of two or more kinds.

In the present invention, when a mixture of a green pigment system and a yellow pigment system is used, 90 parts by weight or less of the yellow pigment system is used based on 100 parts by weight of the total amount of the green pigment system and the yellow pigment system. preferable.

The resin used in the green resin composition used in the present invention is not particularly limited as long as it has pigment dispersibility when used as a colored image forming material.
Those having a film forming property are preferable, and those having a developing property without hindering the photosensitivity are preferable. As such a resin, carboxymethylhydroxyethylcellulose, cellulose resins such as hydroxyethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and the like can be used, but methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate Homopolymer or copolymer of acrylate or methacrylate such as acrylate, propyl acrylate and butyl acrylate, styrene, styrene derivative, and other polymerizable monomers, (meth) acrylic acid (mean acrylic acid and methacrylic acid The same shall apply hereinafter), itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, citraconic acid, citraconic anhydride, citracone Carboxyl group-containing polymerizable monomer and (meth) acrylic acid esters such as monoalkyl esters, styrene, and copolymers of styrene derivatives, other polymerizable monomers are especially preferred.

The monoalkyl maleate is preferably one having 1 to 12 carbon atoms in the alkyl.
Monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate,
Mono n-butyl maleate, mono n-hexyl maleate, mono n-octyl maleate, mono 2-maleate
Examples include ethylhexyl, mono-n-nonyl maleate, and mono-n-dodecyl maleate. As the citraconic acid monoalkyl ester, alkyl having 1 carbon atom
To 12, preferably monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, monoisopropyl citraconic acid, mono-n-butyl citraconic acid, mono-n-hexyl citraconic acid, mono-n-octyl citraconic acid, citraconic acid Mono 2-ethylhexyl, mono-n-nonyl citraconic acid, mono-n-dodecyl citraconic acid and the like can be mentioned. As the styrene derivative, α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-
Hydroxystyrene, 2-hydroxy-4-methylstyrene and the like.

As the resin, a resin having a photopolymerizable unsaturated bond may be used. Preferred examples of such a resin include oxirane rings such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, and monoalkyl glycidyl ether itaconate in a high acid value carboxyl group-containing resin. And one compound having one ethylenically unsaturated bond, allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, N- Free isocyanate is added to a resin obtained by reacting a compound having one ethylenically unsaturated bond (unsaturated alcohol) such as methylol acrylamide or a carboxyl group-containing resin having a hydroxyl group. Unsaturated with conjugated diene polymer or conjugated diene copolymer, conjugated diene polymer or conjugated diene copolymer A resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product with a dicarboxylic anhydride is exemplified.

The unsaturated equivalent of these resins is from 200 to
3,000, preferably 230 to 1,
000, more preferably 250 to
750 is preferable. When the unsaturated equivalent is too small, the photosensitive material tends to be partially cured during the preparation of the photosensitive material, particularly when the pigment is dispersed in the resin, and when the unsaturated equivalent is too large, the photopolymerizability due to the introduction of the unsaturated group is sufficiently high. Not granted. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.

When the above resin has photopolymerizability itself, or when it is given photosensitivity as a composition such as a photosensitive green resin composition as described later, it has an alkali developability after exposure. From the viewpoint of having an acid value of 20 to
It is preferably in the range of 300, more preferably 40 to 2
00, preferably from 60 to 170
Is preferably within the range. If the acid value is too low, alkali developability tends to decrease, and if it is too high, the shape of the image pattern after alkali development tends to be unclear.

The weight average molecular weight of the resin is
It is preferably in the range of 1,500 to 200,000, more preferably in the range of 5,000 to 100,000, and particularly preferably in the range of 10,000 to 50,000. Weight average molecular weight of 1,50
If it is less than 0, the dispersion stability of the pigment tends to decrease, and if it exceeds 200,000, the viscosity becomes high when it is made into a photosensitive liquid, and the coatability, especially the coatability when spin-coating, tends to decrease. is there.

Here, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene.

As the resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000, particularly, a resin represented by the following general formula (II):

[0033]

Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms) and the following general formula (I
II)

[0034]

Embedded image (However, in the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ⁶ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 1
2 represents an alkyl group. )
The repeating unit represented by the general formula (II) / the general formula (II
The repeating unit (molar ratio) represented by I) is 1/1 to 5 /
Resins having a ratio of 1 are preferred in terms of pigment dispersion stability and photosensitivity.

The following are more preferred as the resin. That is, (i) In general formula (III), R
⁴ is a group having a photoreactive unsaturated bond, R ⁵ is a hydrogen atom, R
A repeating unit wherein ⁶ is a hydrogen atom, (ii) a compound represented by the general formula (I
In II), R ⁴ is a group having a photoreactive unsaturated bond, R ⁵ is a hydrogen atom or a group having a photoreactive unsaturated bond, a repeating unit in which R ⁶ is a hydrogen atom, and (iii) a compound represented by the general formula (III) Wherein R ⁴ is a group having a photoreactive unsaturated bond, R ⁵ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ⁶ is a hydrogen atom. , (Iv) In formula (III), R ⁴ and R ⁵ are each independently a hydrogen atom or a group having a photoreactive unsaturated bond, and at least one of them has a photoreactive unsaturated bond. It is preferable that R ⁶ has a repeating unit in which R ⁶ is an alkyl group having 1 to 12 carbon atoms.

The above general formulas (II) and (III)
As a method for producing a resin having a repeating unit represented by the following formula, for example, a precursor of a resin having a repeating unit represented by the general formula (II) or (III) may be added to an unsaturated alcohol (allyl alcohol, -Buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, etc.) by esterification reaction; And a compound having one oxirane ring and one ethylenically unsaturated bond (glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl) as a precursor of the resin having a repeating unit represented by general formula (III). Acrylate, Crotonig Ethers, such as a method of manufacturing by adding itaconic acid monoalkyl monoglycidyl ester, etc.).

As the precursor of the resin having the repeating units represented by the general formulas (II) and (III), styrene or a derivative thereof, maleic acid monoalkyl ester (maleic acid half ester), citraconic acid Monoalkyl ester (half ester of citraconic acid)
Can be obtained by copolymerizing

Examples of the styrene derivative include α-methylstyrene, m or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like.

Examples of the monoalkyl maleate include monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isopropyl maleate, mono-n-butyl maleate, and mono-n-hexyl maleate. And mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like.

Examples of the monoalkyl citraconic acid ester include monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, mono-isopropyl citraconic acid, mono-n-butyl citraconic acid and mono-n-hexyl citraconic acid. Mono-n-octyl citraconic acid, mono-2-ethylhexyl citraconic acid, mono-n-nonyl citraconic acid, mono-n-dodecyl citraconic acid, and the like.

As the resin used in the green resin composition of the present invention, the above-mentioned general formula (II) and general formula (I)
When a resin having a repeating unit represented by II) is used, another resin may be used in combination. As other resins,
Among the above-mentioned resins, resins other than those having the repeating units represented by the above-mentioned general formulas (II) and (III) are used, and further, acrylic resins, epoxy resins, urethane resins, melamine resins and the like May be used. Other resins are 50 parts per 100 parts by weight of total resin.
It is preferred to use it in parts by weight or less.

The green resin composition may further contain a monomer having at least one photopolymerizable unsaturated bond in the molecule, a photoinitiator, etc. to form a photosensitive green resin composition. A photosensitive solution can be prepared by incorporating an organic solvent.

The photopolymerizable unsaturated bond used in the above-mentioned colored image forming material or colored image forming photosensitive solution has one molecule in its molecule.
Among the monomers having at least one, a monomer having one photopolymerizable unsaturated bond in the molecule includes alkyl methacrylates such as methyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Alkyl acrylates, aralkyl methacrylates such as benzyl methacrylate, aralkyl acrylates such as benzyl acrylate, alkoxyalkyl methacrylates such as butoxyethyl methacrylate,
Alkoxyalkyl acrylates such as butoxyethyl acrylate, aminoalkyl methacrylates such as N, N-dimethylaminoethyl methacrylate, aminoalkyl methacrylates such as N, N-dimethylaminoethyl methacrylate, ethyldiethylene glycol methacrylate, butyltriethylene glycol methacrylate;
Alkyl polyalkylene glycol methacrylate such as methyl dipropylene glycol methacrylate, ethyl diethylene glycol, butyl triethylene glycol acrylate, alkyl polyalkylene glycol acrylate such as methyl dipropylene glycol acrylate, aryl polyalkylene glycol methacrylate such as phenyl hexaethylene glycol methacrylate,
Aryl polyalkylene glycol acrylate such as phenylhexaethylene glycol acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, isobornyl methacrylate, methoxylated cyclodecatriene methacrylate, isobornyl acrylate, methoxylated cyclodecatriene acrylate, glycerol methacrylate Fluorinated alkyl methacrylates such as glycerol acrylate and heptadecafluorodecyl methacrylate, fluorinated alkyl acrylates such as heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate.

Among monomers having one or more photopolymerizable unsaturated bonds in the molecule, two or more photopolymerizable unsaturated bonds in the molecule are used.
As the monomer having at least one, bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pen Methacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate,
Polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol Hexaacrylate, dipentaerythritol pentaacrylate and the like can be mentioned.

The monomer having two or more photopolymerizable unsaturated bonds in a molecule further includes a compound represented by the general formula (a):

[0046]

Embedded image (Wherein R represents an ethylene group or a propylene group, a and b each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of bisphenol A represented by the general formula (b):

[0047]

Embedded image (Wherein, c and d each independently represent 1 to 20)
An epichlorohydrin modified product of bisphenol A and an addition ester compound of acrylic acid,
Bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, general formula (c)

[0048]

Embedded image (Wherein, R represents an ethylene group or a propylene group, e and f each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of phosphoric acid represented by the general formula (d )

[0049]

Embedded image (Where g and h are each independently 1 to 10
Epoxide hydrin modified phthalic acid and addition esterified acrylic acid, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol diacrylate represented by the general formula (e):

[0050]

Embedded image (Where i and j are independently 1 to 20
An epicuhydrhydrin modified product of 1,6-hexanediol and an addition esterified product of acrylic acid (having two acryloyl groups in one molecule) represented by
Trimethylolpropane triacrylate, pentaerythritol triacrylate, general formula (f)

[0051]

Embedded image (Wherein, R represents an ethylene group or a propylene group, and three k's each independently represent an integer of 1 to 20), a triacrylate of an alkyne oxide adduct of phosphoric acid represented by the general formula ( g)

[0052]

Embedded image (Wherein, R represents an ethylene group or a propylene group, p, q and r each independently represent an integer of 1 to 20) triacrylate or tris of an alkylene oxide adduct of trimethylolpropane (Methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like. These monomers can be used alone or in combination of two or more.

Examples of the photoinitiator used in the colored image forming material or the colored image forming photosensitive solution include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4. '-Dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholino-1-propanone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4- Naphthoquinone, 9,10-phenanthraquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone,
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and the like. These photoinitiators can be used alone or in combination of two or more.

Examples of the organic solvent used in the photosensitive solution for forming a colored image of the present invention include ketone compounds, alkylene glycol ether compounds, alcohol compounds, aromatic compounds, and lactones. Specifically, ketone compounds include acetone, methyl ethyl ketone, cyclohexanone, dioxane and the like, and alkylene glycol ether compounds include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl. Mono- or dialkyl ethers of diethylene glycol such as ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Acetylated products of diethylene glycol monoalkyl ethers such as ethyl monopropyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether , Triethylene glycol methyl ethyl ether,
Triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, Propylene glycol mono- or dialkyl ethers such as propylene glycol methyl ethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether There are acetylated products of propylene glycol monoalkyl ether such as teracetate and propylene glycol monobutyl ether acetate, and the alcohol compounds include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol and the like. There are benzene, toluene, xylene and the like as aromatic compounds, and β-lactone, γ-
Lactone, δ-lactone, and the like, and other examples thereof include organic solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, 3-methyl-3-methoxybutyl acetate, and ethyl acetate. . These can be used alone or in combination of two or more.

Among these organic solvents, diethylene glycol mono- or dialkyl ethers, diethylene glycol monoalkyl ether acetylates, triethylene glycol mono- or dialkyl ethers, propylene glycol mono- or dialkyl ethers, propylene glycol monoalkyl ether acetylates, Lactone compounds are particularly preferred in terms of pigment dispersibility, coating film appearance, and image pattern resolution.

The resin, pigment, monomer having at least one photopolymerizable unsaturated bond in the molecule, and the photoinitiator used in the photosensitive green resin composition or the photosensitive liquid for forming a green pixel are as follows. Based on the total amount, (a) the resin is preferably 10 to 85% by weight, more preferably 20 to 60% by weight, particularly preferably 25 to 50% by weight, and (b) the pigment is
Preferably 5 to 50% by weight, more preferably 10 to 40%
% By weight, particularly preferably 15 to 30% by weight, and (c) a monomer having one or more photopolymerizable unsaturated bonds in a molecule.
Preferably 2 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 10 to 35% by weight, (d) the photoinitiator is preferably 0.01 to 20% by weight, more preferably 2 to 15% by weight. % By weight, particularly preferably 5 to 10% by weight.

If the amount of the resin in the photosensitive green resin composition or the photosensitive liquid for forming a green pixel is too small, the dispersion stability of the pigment tends to decrease. If the amount is too large, the viscosity of the photosensitive liquid becomes high. There is a tendency that the coatability, particularly the coatability during spin coating, decreases.

When the amount of the pigment is too small, the color density of the image tends to decrease, and when the amount is too large, the light sensitivity tends to decrease.

When the amount of the monomer having one or more photopolymerizable unsaturated bonds in the molecule is too small, the photosensitivity tends to decrease, and when the amount is too large, the dispersion stability of the pigment tends to decrease.

Further, when the amount of the photoinitiator is too small, the photosensitivity tends to decrease, and when the amount is too large, the adhesiveness tends to decrease.

The organic solvent is a resin having a total solid content of 5 to 40% by weight including a resin, a pigment, a monomer having at least one photopolymerizable unsaturated bond in a molecule and a photoinitiator in a green pixel forming photosensitive solution. Preferably, it is used so as to fall within the range. If the total solid content exceeds 40% by weight, the viscosity tends to be high and the applicability tends to be poor. If the total solid content is less than 5% by weight, the viscosity tends to be low and the applicability tends to be poor.

The photosensitive green resin composition or the photosensitive liquid for forming a green pixel of the present invention contains a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for suppressing a dark reaction, Silane coupling agent (having vinyl group, epoxy group, amino group, mercapto group, etc.) and titanate coupling agent (isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate) Etc.), and surfactants (fluorine-based, silicon-based, hydrocarbon-based, etc.) for improving the smoothness of the film and other various additives such as ultraviolet absorbers and antioxidants are appropriately used as necessary. be able to.

Next, a method for producing the green resin composition, the photosensitive green resin composition and the photosensitive liquid for forming a colored image used in the present invention will be described.

The pigment is mixed and dispersed with a resin, an organic solvent and, if necessary, a dispersant. At this time, the mixture is preferably subjected to dispersion treatment by kneading using a dispersing / kneading apparatus such as an ultrasonic dispersing machine, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader. At this time, it is preferable to use at least 20 parts by weight of the resin with respect to 100 parts by weight of the pigment. If the amount of the resin is too small, the dispersion stability of the pigment tends to decrease.
It is preferable to use at least 100 parts by weight of the organic solvent at the time of dispersion with respect to 100 parts by weight of the pigment and the resin at the time of dispersion. If it is less than 100 parts by weight, the viscosity at the time of dispersion is too high, and dispersion may be difficult particularly when the dispersion is carried out by a ball mill, a sand mill, a bead mill or the like. As described above, a green resin composition can be produced.

In order to prepare a photosensitive green resin composition and a photosensitive liquid for forming a green image, a monomer having at least one photopolymerizable unsaturated bond in a molecule and a photoinitiator are mixed. Mixing may be performed before the dispersion treatment, or may be performed after the dispersion treatment. The whole amount of the resin may not be used at the time of the dispersion, and the remainder may be mixed later, particularly at the time of producing the colored image forming photosensitive liquid.

The amount of each component used is adjusted from the time of production of the green resin composition so that it finally becomes the compounding ratio in the photosensitive green resin composition and the photosensitive liquid for forming a green image.

Examples of the dispersant include anionic dispersants such as polycarboxylic acid type polymer surfactants and polysulfonic acid type polymer surfactants; nonionic dispersants such as polyoxyethylene / polyoxypropylene block polymers; An organic dye derivative such as an anthraquinone-based, perylene-based, phthalocyanine-based, or quinacdrine-based organic dye into which a substituent such as a carboxyl group, a sulfonate group, a carboxylic acid amide group, or a hydroxyl group is introduced. It is preferable because the dispersibility and dispersion stability of the pigment are improved. The content of the pigment dispersant and the derivative of the organic dye is preferably 50 parts by weight or less based on 100 parts by weight of the pigment. If it exceeds 50 parts by weight, the chromaticity tends to shift.

In the dispersion treatment, the entire amount of the resin may be used together with the pigment at the time of the dispersion treatment, or a part of the resin may be added after the dispersion treatment. However, it is preferable to use at least 20 parts by weight of the resin for 100 parts by weight of the pigment during the dispersion treatment. If it is less than 20 parts by weight, the dispersion stability of the pigment tends to decrease.

Similarly, the entire amount of the organic solvent may be used together with the pigment at the time of the dispersion treatment, or a part of the organic solvent may be added after the dispersion treatment. However, it is preferable to use at least 100 parts by weight of the organic solvent at the time of the dispersion treatment, based on 100 parts by weight of the total amount of the pigment and the resin at the time of the dispersion treatment. 100
If the amount is less than part by weight, the viscosity of the dispersion-processed character is too high, and particularly when the dispersion is performed by a ball mill, a sand mill, a bead mill, or the like, it may be difficult to perform dispersion.

In producing the color filter of the present invention, each pigment system suitable for a colored image such as red, green, blue and black is used.

When the photosensitive colored resin composition of the present invention or the photosensitive liquid for forming a colored image is used for producing a color filter, each pigment system suitable for a colored image such as red, green, blue or black is used. Can be The above-mentioned green pigments are used, but the following pigments are used as other pigments.

For a red colored image, a single red pigment system may be used, or a yellow pigment system or an orange pigment system may be mixed with a red pigment system for toning.

Examples of red pigments include, for example, Pigment Red 9, 123, 155, 1
68, 177, 180, 217, 220, 224, 25
4 and the like.

Examples of yellow pigments include, for example, Pigment Yellow 17, 20, 24, and 8 under the color index name.
3, 93, 109, 110, 117, 125, 128,
129, 138, 139, 147, 150, 154 and the like.

As the orange pigments, for example, Pigment Orange 43, 71 or the like by a color index name can be mentioned.

These red pigments, yellow pigments and orange pigments can be used as a mixture of two or more kinds. When a mixture of a red pigment system and a yellow pigment system or an orange pigment system is used, the yellow pigment system or the orange pigment system is used in an amount of 100 parts by weight based on the total amount of the red pigment system and the yellow pigment system or the orange pigment system. It is preferred to use it in a weight part or less.

As the blue colored image, a single blue pigment system may be used, or a violet pigment system may be mixed with a blue pigment system for toning.

Examples of blue pigments include, for example, Pigment Blue 15, 15: 3 and 15:
4, 15: 6, 22, 60 and the like.

Examples of purple pigments include, for example, Pigment Violet 19, 23, 2
9, 37, 50 and the like.

These blue pigments and purple pigments can be used as a mixture of two or more kinds. When a mixture of a blue pigment and a violet pigment is used, it is preferable to use 90 parts by weight or less of the violet pigment based on 100 parts by weight of the total of the blue pigment and the violet pigment.

For the black colored image, for example, black pigments such as carbon black, graphite, titanium carbon, black iron oxide, and manganese dioxide are used.

Formulation of a colored resin composition, a photosensitive colored resin composition and a photosensitive liquid for forming a colored image when a pigment system other than the green pigment system is used, and preparation of components, compositions or photosensitive solutions other than pigments The method and the like are determined according to the green resin composition, the photosensitive green resin composition, and the photosensitive liquid for forming a green image.

In order to laminate a photosensitive layer on a substrate using a colored image forming material, a colored image forming photosensitive liquid is directly applied to a substrate, or the photosensitive liquid is once applied to a support to form a film. And lamination on a substrate.

The above-mentioned substrate is selected depending on the application. For example, a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass or the like, or a synthetic resin such as polyester resin, polycarbonate resin, acrylic resin, vinyl chloride resin, etc. Examples include a sheet, a film or a plate, a metal substrate such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate, a ceramic plate, and a semiconductor substrate having a photoelectric conversion element. On these substrates, a black matrix may be formed in advance by chromium evaporation or the like.

Examples of the method of applying the photosensitive liquid to the substrate include roll coater coating, spin coater coating, spray coating, whey coater coating, dip coater coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, air knife coater coating, and the like. There is.

After the application, the temperature is usually 1 to 50 ° C. to 130 ° C.
It is preferable to obtain a film by drying for up to 30 minutes. Thus, a film composed of the colored image forming material can be obtained.

The thickness of the photosensitive layer formed in this manner is appropriately determined depending on the application, but is usually 0.1 to 300.
It is preferably used in the range of μm. When used for a color filter, the thickness is preferably in the range of 0.2 to 5 μm.

A photosensitive layer can be formed on a support in the same manner as described above. In order to laminate this photosensitive layer on the substrate, it is preferable that the film is superposed on the substrate and pressure-bonded through a roller under reduced pressure. The support is preferably peeled off after the photosensitive layer is laminated on the substrate. As the support, a polyethylene film, an acrylic resin film, a polyester film, or the like can be used.

The exposure of the photosensitive layer laminated on the substrate can be performed by irradiating the photosensitive layer with actinic rays in an image-like manner. Thereby, the film in the exposed portion can be cured. At the time of exposure, an oxygen barrier film such as polyvinyl alcohol may be formed on the surface of the film with a thickness of 0.5 to 30 μm, and the film may be exposed from above.

As the light source of the actinic ray, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a visible light laser and the like are suitable. Using these light sources, actinic rays are irradiated imagewise by pattern exposure through a photomask, direct drawing by scanning, or the like.

Following the above exposure, a developing step is performed to remove unexposed portions. As a developing method, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
An aqueous solution containing an inorganic alkali such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium metasilicate, or the like, an organic base such as monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-butylamine, or a salt (alkali development Liquid), an unsolved portion is removed by spraying a developer such as an organic solvent or dipping in a developer to obtain a colored image pattern of a cured film corresponding to an image.

After development, post-baking is preferably performed to further harden the colored image pattern. The post-bake temperature is preferably from 60 to 280C, and the heating time is preferably from about 1 to 60 minutes.

A colored image is formed by such a colored image forming step. In particular, in a method of manufacturing a color filter, the colored image forming step is performed for three to four different colored images including a green image forming step. It is preferable to repeat. For example, a red, green, and blue colored image is formed on a black matrix previously formed by chromium evaporation or the like. After forming a black matrix using a black colored image forming material, red, green and blue colored images are formed. Further, after forming red, green, and blue colored images, a black matrix is formed using a black image forming material in a gap between the colored images. The order of forming the red, green, and blue colored images is arbitrary. The colored image is adapted to form pixels for each color.

[0094]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. (1) Resin to be used: a copolymer composed of 50 mol% of styrene-20 mol% of maleic acid monopropyl ester-30 mol% of maleic acid derivative, having a weight average molecular weight of 11,000 and an acid value of 65 (hereinafter referred to as copolymer) (2) The repeating unit based on the maleic acid derivative has the following structure.

[0095]

Embedded image Example 1 (1) Production of Photosensitive Liquid for Green Image Formation 60 g of copolymer A as a resin and formula (IV) as a pigment
22 g of a green pigment represented by C.I. I. Pigment Yellow 150 and 250 g of diethylene glycol dimethyl ether were mixed, and the resulting mixture was subjected to a dispersion treatment using a bead mill for 2 hours. The obtained dispersion liquid 22
0 g, 35 g of dipentaerythritol hexaacrylate as a monomer, and benzophenone 6 as a photoinitiator.
g, 3 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 125 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a photosensitive liquid for green image formation.

[0096]

Embedded image (2) Production of Colored Image This photosensitive liquid was applied to a glass substrate (manufactured by Asahi Glass Co., Ltd., trade name AN6).
35) was applied by spin coating and dried at 80 ° C. for 5 minutes to form a film having a thickness of 2.0 μm.

The obtained film was exposed to an image of 400 mJ / cm ² through an ultra-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 0.3% by weight of potassium hydroxide. Table 1 and FIG. 1 show the transmittance, chromaticity, and transmission curve of the obtained green pixel.

Example 2 (1) Production of Photosensitive Liquid for Forming Green Image 60 g of copolymer A as a resin, 21 g of a green pigment represented by formula (V) as a pigment, C.I. I. Pigment Yellow 150 and 250 g of diethylene glycol dimethyl ether were mixed, and the resulting mixture was subjected to a dispersion treatment using a bead mill for 2 hours. The obtained dispersion liquid 220
g, 35 g of dipentaerythritol hexaacrylate as a monomer and 6 g of benzophenone as a photoinitiator
Then, 3 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 125 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a photosensitive liquid for forming a green image.

[0099]

Embedded image (2) Production of Colored Image This photosensitive liquid was applied to a glass substrate (manufactured by Asahi Glass Co., Ltd., trade name AN6).
35) was applied by spin coating and dried at 80 ° C. for 5 minutes to form a film having a thickness of 2.0 μm.

The obtained film was exposed to an image of 400 mJ / cm ² through an ultra-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 0.3% by weight of potassium hydroxide. Table 1 shows the transmittance and chromaticity of the obtained green pixels.

Example 3 (1) Production of red colored resin composition and photosensitive solution 40 g of copolymer A as resin and C.I. I. Pigment Red 177, 25 g of C.I. I. Pigment Yellow 139 and 200 g of diethylene glycol dimethyl ether were mixed, and the resulting mixture was subjected to a dispersion treatment using a bead mill for 2 hours. The resulting dispersion 200
g, 13 g of copolymer A, 27 g of dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone as a photoinitiator and N, N'-tetraethyl-
2,4 g of 4,4'-diaminobenzophenone and 292 g of diethylene glycol dimethyl ether as an organic solvent
Was added and mixed to obtain a photosensitive liquid for forming a colored image.

(2) Production of Blue Colored Resin Composition and Photosensitive Liquid 20 g of copolymer A as a resin and C.I. I. Pigment Blue 15: 6, 24 g, C.I. I. Pigment Violet 23 and 216 g of diethylene glycol dimethyl ether were mixed, and the resulting mixture was subjected to dispersion treatment using a bead mill for 2 hours. To 140 g of the obtained dispersion, 38.5 g of copolymer A, 35 g of dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone as a photoinitiator, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 2 g of organic 262.5 g of diethylene glycol dimethyl ether as a solvent was added and mixed to obtain a photosensitive liquid for forming a colored image.

(3) Production of Color Filter A green image pattern was formed on a glass substrate having a black matrix formed of chromium by the same method and under the same conditions as in Example 1, and then heated at 240 ° C. for 30 minutes. . Next, a red image pattern is formed next to the green pixel pattern under the same method and conditions as in Example 1 using the above-described red image forming photosensitive liquid.
Heated for minutes. Next, a blue image pattern is formed next to the green pixel pattern under the same method and conditions as in Example 1 using the above-described blue image forming photosensitive liquid.
Heating was performed at 40 ° C. for 30 minutes. From the above, a color filter in which one pixel was arranged in a stripe shape of 80 μm × 240 μm consisting of three colors of green, red and blue was created.

Comparative Example (1) Production of Photosensitive Liquid for Forming Green Image 60 g of copolymer A as a resin and formula (VI) as a pigment
20 g of a green pigment represented by C.I. I. Pigment Yellow 150 and 250 g of diethylene glycol dimethyl ether were mixed, and the resulting mixture was subjected to a dispersion treatment using a bead mill for 2 hours. The obtained dispersion liquid 22
0 g, 35 g of dipentaerythritol hexaacrylate as a monomer, and benzophenone 6 as a photoinitiator.
g, 3 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 125 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a green image forming photosensitive liquid.

[0105]

Embedded image (2) Production of Colored Image This photosensitive liquid was applied to a glass substrate (manufactured by Asahi Glass Co., Ltd., trade name AN6).
35) was applied by spin coating and dried at 80 ° C. for 5 minutes to form a film having a thickness of 2.0 μm.

The obtained film was exposed to an image of 400 mJ / cm ² through an ultra-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 0.3% by weight of potassium hydroxide. Table 1 and FIG. 1 show the transmittance, chromaticity, and transmission curve of the obtained green pixel.

[0107]

[Table 1] The transmittance and the chromaticity were measured using a spectral colorimeter JP7200F manufactured by Color Techno System Co., Ltd. Y, x of measured value
And y are XYZ (Yx
y) Y value, x value and y value based on the color system.

Table 1 shows that the use of copper phthalocyanine having a high bromination ratio (addition number: 15 to 16) as the green pigment increases the chromaticity Y value and improves the color purity (Examples 1 and 2). On the other hand, when the number of added bromine is 12 (Comparative Example), it is recognized that the Y value of the chromaticity is low and the color purity is not good.

FIG. 1 shows a transmission curve of a green pixel, and a curve 1 represents a transmission curve of a green pixel and a curve 2 of the first embodiment.
Shows the transmission curve of the green pixel of the comparative example. As is clear from FIG. 1, the light transmittance of Example 1 is superior to that of Comparative Example.

A color filter prepared using a green photosensitive liquid having a higher light transmittance than ever before (Example 3)
Has excellent optical characteristics and is effective as an image display device.

[0111]

The green image based on the green resin composition of the present invention, the photosensitive green resin composition of the present invention and the photosensitive liquid for forming a green image of the present invention has excellent light transmittance.

According to the method for producing a colored image of the present invention, a green image having excellent light transmittance can be obtained.

According to the method for producing a color filter of the present invention, a color filter having a green image with excellent light transmittance can be produced.

[Brief description of the drawings]

FIG. 1 is a graph showing light transmittance of a green pixel.

[Explanation of symbols]

 1 Green pixel light transmittance curve created in Example 1 2 Green pixel light transmittance curve created in Comparative example

Continuing on the front page (72) Inventor Koji Yamazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture Inside the Goi Works of Hitachi Chemical Co., Ltd. (72) Inventor Seiji Haruhara 14 Goi South Coast, Ichihara City, Chiba Prefecture In-house (72) Inventor Tetsuya Okazaki 14 Goi Minami Coast, Ichihara-shi, Chiba Hitachi Chemical Industry Co., Ltd. Goi Office (72) Inventor Seigo Yokochi 14 Goi-minamikaigan, Ichihara-shi, Chiba Prefecture F-term (reference) 2H025 AA00 AB13 AC01 AC08 AD01 BC31 CA00 CB00 CC03 CC12 2H048 BA45 BA48 BB42 BB46 4J002 AB021 AC021 BC031 BE021 BG011 BG041 BG042 BG051 BG052 BH011 BH021 CD191 CK021 EB EG037 EB037

Claims (8)

[Claims] 1. A green resin composition comprising a green pigment dispersed in a resin, wherein the green pigment has the general formula (I): (Wherein, X represents a hydrogen atom, a chlorine atom or a bromine atom), wherein the number of bromine atoms is 14 or more and 16 or less. 2. A green resin composition comprising a green pigment and a yellow pigment dispersed in a resin, wherein the green pigment has the general formula (I)
Wherein the number of bromine atoms is 14 or more and 16 or less. 3. A photosensitive green resin composition comprising a green pigment, a resin, a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator, wherein the green pigment has the general formula (I) Wherein the number of bromine atoms is 14 or more and 16 or less. 4. A photosensitive green resin composition comprising a green pigment, a yellow pigment, a resin, a monomer containing at least one photopolymerizable unsaturated bond in a molecule and a photoinitiator, wherein the green pigment is generally used. A photosensitive green resin composition represented by the formula (I), wherein the number of bromine atoms is 14 or more and 16 or less. 5. A green image forming material comprising the photosensitive green resin composition according to claim 3 or 4, further comprising an organic solvent, wherein components other than the organic solvent are dissolved or dispersed in the organic solvent. Photosensitive liquid. 6. A method for producing a colored image, comprising a step of laminating a photosensitive layer comprising the photosensitive green resin composition according to claim 3 on a substrate and exposing and developing the layer. 7. The method for producing a colored image according to claim 6, wherein the photosensitive layer is formed from the photosensitive liquid according to claim 5. 8. A method for producing a color filter, comprising a step of forming a green image by the method for producing a colored image according to claim 6.